CN106220835A - Low terminal carboxy content polyester of organic amine end-blocking and preparation method thereof - Google Patents
Low terminal carboxy content polyester of organic amine end-blocking and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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Abstract
The invention discloses the low terminal carboxy content polyester of a kind of organic amine end-blocking, the raw material of following quality proportioning be prepared from: dicarboxylic acid monomer 10,000 18000, ethylene glycol 1,800 6500, catalyst 1 10, stabilizer 2 10, opening agent 2 50, organic amine 1.3 7.5.The mylar of the present invention has good colour, barrier property, thermal stability and wet and heat ageing resistant performance, can increase the service life, there is higher hot strength, excellent size stability simultaneously, can be widely used for the field such as construction substrate, solar cell backboard.
Description
Technical field
The present invention relates to polyester synthesis technical field, particularly relate to the low terminal carboxy content polyester of a kind of organic amine end-blocking,
And manufacture method.
Background technology
Biaxially oriented polyester film (BOPET) has much excellent physics and chemical characteristic mechanical strength is high, optical
Energy is excellent, good barrier property, electrical insulation capability are good, use temperature width (-70 ~ 200 DEG C), chemical resistance and dimensional stability good
Good, therefore have been widely used at aspect tools such as electronics, electrical equipment, packaging, Plate making printing and sensitive materials.2008, the whole world was poly-
Ester film aggregated capacity is estimated as 290-300 ten thousand tons, it is contemplated that the aggregated capacity of 2009 is about at about 3,200,000 tons, wherein: China is existing
Production capacity plus the anticipated new production line production capacity nearly 900,000 tons gone into operation in 2009, height occupies first place in the world, it has also become whole world polyester
The big production base of the first of film product.But polyester material is during processing, storing and use, due to by internal and external factor
The comprehensive function of (including light, heat, humidity, mechanical pressure) etc., polyester material performance is gradually reduced, and uses function so that losing.
By the research to polyester ageing process, suitable anti-aging and modified measures can be taked, improve the ageing-resistant property of material
Can, the speed of delaying aging, to reach the purpose increased the service life, this is also one of approach solving white pollution.
End carboxyl is one quality index of polyester resin, and control of product quality requires less than 30 mol/t.It is as quality
Con trolling index is to resin quality, performance important.The height of carboxyl end group value, directly affects the thermally-stabilised of polyester slice
Property, thus affecting the spinning quality of section, it can cause resin heat stability to be deteriorated, it is easy to degraded, and impact uses.Meanwhile, acid
Be esterification catalyst, i.e. the generation of end carboxyl can carry out catalytic degradation reaction to PET strand again, and so forth, is produced from
Catalytic effect.The low value-added polyester slice that polyester producer of China goes into operation at present, carboxyl end group value is the highest.For many years, fall
Low section middle-end carboxyl value, improves polyester product quality, always polyester synthesis industry and is eager and insoluble problem.
Organic amine generally refers to, as organic amine, the organic species that organic species generates with ammonia generation chemical reaction.
It is divided into seven big classes, fatty amines, alcamines, amide-type, alicyclic ring amine, aromatic amine, naphthalene system amine, other amine etc..Wherein,
The reasons such as alcamines is due to good with the polyester system compatibility, and fusing point is low, and boiling point is high, good stability are chosen as polyester synthesis end-blocking
Agent.Process of polyester synthesizing carries out reacting with end carboxyl and blocks into salt, prevent further autocatalytic effect thus reduce
Polyester depolymerization and content of carboxyl end group.
If Chinese patent CN 101011332(M rope, C Bernard Chevallier, A-L dagger-axe Delhi.Based on ester end-blocking poly-
Aqueous fluid light protection compositions [P] of esteramides polymer.China, 2007, CN 101011332) disclose one at least
Polyesteramide (ETPEA) polymer of kind of ester end-blocking in fluid composition, be used for increasing SPF (sun protection factor) (SPF) and/or reduce or
Even eliminating the purposes of fluffing effect, wherein said compositions at least contains one in cosmetically acceptable aqueous carrier and can shield
Cover purple extraradial light protection system.
Pan Cork, Chinese patent CN 105683239 A(J J Shandong, A A Malin, D E Wei Aidi.Epoxy radicals
The polyester [P] of end-blocking.China, 2016, CN 105683239 A) disclose a kind of polyester material with epoxide group end-blocking.
Chemistry itself can be carried out instead owing to the compound of epoxy radicals end-blocking is applicable to multiple purpose, the such as compound of epoxy radicals end-blocking
Or should react with one or more co-reactants and form the polymer with high molecular and/or crosslinking.So this base polymer
It is commonly available to one or more in multiple purpose, is used for example as sticker.
Chinese patent CN 105504238 Zhao A(three is flat, Gao Jun, Zhao Hui.A kind of polyester plasticising of monobutyl ether alcohol end-blocking
The preparation method [P] of agent.China, 2016, CN 105504238 A) disclose a kind of only son in polymeric material additive agent field
The preparation method of the polyester plasticizer of base ether alcohol end-blocking, its preparation process mainly comprises the steps that at water entrainer and catalyst
Under effect, the dicarboxylic acids of excess first obtains terminal carboxyl polyester through polycondensation reaction with dihydroxylic alcohols；State then up in product
Add monobutyl ether alcohol, carry out esterification end-blocking；Through decompression distillation after, steam water entrainer and excessive unreacted monobutyl
Ether alcohol, i.e. obtains the polyester of monobutyl ether alcohol end-blocking.Use the monobutyl ether alcohol end-blocking that this inventive technique scheme prepares
Polyester plasticizer, there is the low volatility of polyester plasticizer, heat-resist, low temperature flexibility good, durability and resistance to oil extraction
Etc. advantage, have the good compatibility of monobutyl ether alcohol and the feature of compliance concurrently simultaneously, also there is viscosity adjustability.This method
Resulting materials is mainly as a kind of nontoxic, environment-friendlyplasticizer plasticizer being applicable to the polymeric materials such as plastics, rubber, binding agent.
Chinese patent CN 104974351 A(king Guiyou, Nie Zubao, Jing Hao.A kind of phosphorous-containing polyester of carboxy blocking and
Preparation method and application [P].China, 2015, CN 104974351 A) disclose phosphorous-containing polyester and the system thereof of a kind of carboxy blocking
Preparation Method and application, with phenolic hydroxyl group end-blocking phosphorous-containing polyester, alkylene oxides monomer, anhydrides as reaction raw materials, synthesized carboxyl
The phosphorus-containing polyester fire retardant type firming agent of end-blocking.By preparing flame retardant type firming agent, and by fire-retardant in Curing Process of Epoxy
Type firming agent is incorporated in epoxy-resin systems, has prepared the epoxy resin of high flame retardant, and does not affect epoxy resin its
His performance.
But there is presently no the report in terms of organic amine prepares low terminal carboxy aging resistance polyester as end-capping reagent.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, propose the low terminal carboxy content polyester of a kind of organic amine end-blocking, thermostability
Can be excellent, manufacture method is simple, and service life is long, can apply under the harsh conditions of high-temperature high-humidity simultaneously.
In order to realize foregoing invention purpose, the present invention provides techniques below scheme: the low terminal carboxy of a kind of organic amine end-blocking
Containing weight polyester, the raw material of following quality proportioning be prepared from: dicarboxylic acid monomer 10000-18000, ethylene glycol 1800-6500,
Catalyst 1-10, stabilizer 2-10, opening agent 2-50, organic amine 1.3-7.5.
Further, dicarboxylic acid monomer is p-phthalic acid.
Further, one or more during catalyst is antimony system, titanium system or germanium series catalysts.
Further, stabilizer is the combination of one or both of phosphoric acid lipid or phosphite apoplexy due to endogenous wind.
Further, one or more during opening agent is barium sulfate, calcium carbonate or silicon dioxide.
Further, one or more during organic amine is triethanolamine, diethanolamine or ethylenediamine.
The preparation method of the low terminal carboxy content polyester of a kind of organic amine described above end-blocking, comprises the following steps:
(1), dioctyl phthalate monomer, ethylene glycol, catalyst, opening agent and stabilizer being mixed in proportion, it is anti-that heating carries out esterification
Should, judge esterification degree by water yield, after esterification reaches more than 95%, terminate esterification；
(2), in step (1) esterification reaction product, add part organic amine, carry out polycondensation reaction under a high vacuum；
, step (2) polycondensation reaction latter stage, add remaining organic amine and block, obtain low terminal carboxy content polyester.
Further, the low terminal carboxy content polyester prepared processes through biaxial tension.
Further, step (2) in, the quality proportioning of organic amine is 0.3-0.5.
Further, step (3) in, the quality proportioning of organic amine is 1-7.
Compared with prior art, the invention have the advantages that by there was added at twice during synthesizing poly-vinegar
Machine amine end-capping reagent, carries out reacting with end carboxyl in process of polyester synthesizing and blocks into salt, prevent further self-catalysis from imitating
Should thus reduce polyester depolymerization and content of carboxyl end group, finally make made low terminal carboxy polyester have good heat resistance, resistance to
Ageing properties, can increase the service life, and has higher hot strength, excellent size stability simultaneously, is completely suitable for building
The field such as base material, solar cell backboard.
Detailed description of the invention
Describing the present invention below in conjunction with embodiment, the description of this part is only exemplary and explanatory, no
Reply protection scope of the present invention has any restriction effect.
Producer, specification and processing method that in the embodiment of the present invention, raw material is selected are as follows:
P-phthalic acid: the happy together safe chemical products company limited in Tianjin, Beijing, purity 99%.
M-phthalic acid: the happy together safe chemical products company limited in Tianjin, Beijing, purity 99%.
Ethylene glycol: Sinopec Beijing Yanshan Mountain branch company, purity 99.8%.
Antimony glycol: Shanghai rain Trade Co., Ltd., 99.9%.
Trimethyl phosphate: Yangzhou Feng Ye Chemical Co., Ltd., 99.5%.
Silicon dioxide opening agent: Dongguan City Bao Sheng plastic cement company limited, 99%.
Ethylene glycol amine: Jiangsu Yonghua Fine Chemical Co., Ltd., 99.8%.
Method of testing and instrument used by the present invention are as follows:
Content of carboxyl end group: survey according to FZ/T 50012-2006 " the mensuration titrimetry of Determining terminal carboxy group in PET "
Examination.
Hot strength, elongation at break: polyester is pressed into the thin slice of 0.2mm, then with special cut-off knife, polyester sheet is cut
Become dumbbell shaped, reference standard GB/T528-2009, universal testing machine is tested the tensile property of polyester sample.Rate of extension is
100mm/min。
80 DEG C of water soak 48h mass change: take polyester sheet and put people and be dried and weigh to the surface plate of constant weight (essence
Really to 0.0001g), then polyester sheet is placed in equipped with in the hermetic container of deionized water, then puts in the baking oven of 80 DEG C
Add heat soaking, be dried after taking-up, be cooled to room temperature, weigh (until weight), calculate mass change.
Heat decomposition temperature: taking a certain amount of polyester print will on the resistance to company's T G 209 F3 type thermogravimetric analyzer of speeding of Germany
Sample is heated to 800 DEG C from room temperature, record decomposition temperature (residual qualities is the time of 95%).
Embodiment 1
The low terminal carboxy content polyester of a kind of organic amine end-blocking, the raw material including following quality proportioning synthesizes: terephthaldehyde
Acid 2000 g, ethylene glycol 900 g, antimony glycol 0.8 g, trimethyl phosphate 1 g, particle diameter is the silicon dioxide opening agent 3 of 5 μm
G, adds diethanolamine 0.1 g for the first time, and second time adds diethanolamine 0.8 g.
The production method of this ageing-resistant polyester of low terminal carboxy content biaxial tension, comprises the following steps:
(1) p-phthalic acid, ethylene glycol, glycol antimony catalyst, silicon dioxide opening agent and stabilizer are weighed in proportion
Mix homogeneously, joins in 5 L reactors, stirs half an hour, is then shut off stirring, opens vacuum system and slowly extracts oxygen in still out
Gas, is then passed through nitrogen and leads to nitrogen 3 times to normal pressure, repetition evacuation, and then pressurization intensification carries out esterification, and reaction temperature is tieed up
Holding at 230-260 DEG C, in still, pressure maintains about 400kPa, judges esterification degree by process tower top water yield,
After esterification reaches more than 95%, esterification terminates, now in still pressure at 20 below kPa, tower top temperature 100 DEG C with
Under；
(2) after esterification terminates, close process tower valve, in loading hopper, add ethylene glycol amine, loading hopper evacuation is led to
Nitrogen three times, opens hopper valve and adds ethylene glycol amine for the first time after then passing to the nitrogen of 150 kPa, the completeest to esterification
Full dioctyl phthalate monomer blocks, and fully opens vacuum pumping valve after the most slowly pressure in still being drawn to-100 kPa
Door, fine vacuum carries out polycondensation reaction, and period temperature in the kettle maintains between 265-270 DEG C；
(3) polycondensation adds ethylene glycol amine latter stage after motor power of agitator reaches certain value again in loading hopper, will charging
Bucket evacuation leads to nitrogen three times, opens hopper valve second time addition ethylene glycol amine and blocks, go out after stirring 2 min after normal pressure
Material, cooling, pelletizing obtain low terminal carboxy content polyester；
(4) gained polyester is obtained low terminal carboxy content polyester after biaxial tension.
Embodiment 2
The low terminal carboxy content polyester of a kind of organic amine end-blocking, the raw material including following quality proportioning synthesizes: isophthalic diformazan
Acid 2000 g, ethylene glycol 900 g, antimony glycol 0.8 g, trimethyl phosphate 1.2 g, particle diameter is the silicon dioxide opening agent 4 of 5 μm
G, adds diethanolamine 0.1 g for the first time, and second time adds diethanolamine 0.8 g.
The production method of this ageing-resistant polyester of low terminal carboxy content biaxial tension, comprises the following steps:
(1) M-phthalic acid, ethylene glycol, glycol antimony catalyst, silicon dioxide opening agent and stabilizer are weighed in proportion
Mix homogeneously, joins in 5 L reactors, stirs half an hour, is then shut off stirring, opens vacuum system and slowly extracts oxygen in still out
Gas, is then passed through nitrogen and leads to nitrogen 3 times to normal pressure, repetition evacuation, and then pressurization intensification carries out esterification, and reaction temperature is tieed up
Holding at 230-260 DEG C, in still, pressure maintains about 400kPa, judges esterification degree by process tower top water yield,
After esterification reaches more than 95%, esterification terminates, now in still pressure at 20 below kPa, tower top temperature 100 DEG C with
Under；
(2) after esterification terminates, close process tower valve, in loading hopper, add ethylene glycol amine, loading hopper evacuation is led to
Nitrogen three times, opens hopper valve and adds ethylene glycol amine for the first time after then passing to the nitrogen of 150 kPa, the completeest to esterification
Full dioctyl phthalate monomer blocks, and fully opens vacuum pumping valve after the most slowly pressure in still being drawn to-100 kPa
Door, fine vacuum carries out polycondensation reaction, and period temperature in the kettle maintains between 265-270 DEG C；
(3) polycondensation adds ethylene glycol amine latter stage after motor power of agitator reaches certain value again in loading hopper, will charging
Bucket evacuation leads to nitrogen three times, opens hopper valve second time addition ethylene glycol amine and blocks, go out after stirring 2 min after normal pressure
Material, cooling, pelletizing obtain low terminal carboxy content polyester；
(4) gained polyester is obtained low terminal carboxy content polyester after biaxial tension.
Embodiment 3
The low terminal carboxy content polyester of a kind of organic amine end-blocking, the raw material including following quality proportioning synthesizes: terephthaldehyde
Acid 2000 g, ethylene glycol 900 g, antimony glycol 1.0 g, trimethyl phosphate 1.5 g, particle diameter is the silicon dioxide opening agent 4 of 5 μm
G, adds diethanolamine 0.2 g for the first time, and second time adds diethanolamine 0.8 g.
The production method of this ageing-resistant polyester of low terminal carboxy content biaxial tension, comprises the following steps:
(1) p-phthalic acid, ethylene glycol, glycol antimony catalyst, silicon dioxide opening agent and stabilizer are weighed in proportion
Mix homogeneously, joins in 5 L reactors, stirs half an hour, is then shut off stirring, opens vacuum system and slowly extracts oxygen in still out
Gas, is then passed through nitrogen and leads to nitrogen 3 times to normal pressure, repetition evacuation, and then pressurization intensification carries out esterification, and reaction temperature is tieed up
Holding at 230-260 DEG C, in still, pressure maintains about 400kPa, judges esterification degree by process tower top water yield,
After esterification reaches more than 95%, esterification terminates, now in still pressure at 20 below kPa, tower top temperature 100 DEG C with
Under；
(2) after esterification terminates, close process tower valve, in loading hopper, add ethylene glycol amine, loading hopper evacuation is led to
Nitrogen three times, opens hopper valve and adds ethylene glycol amine for the first time after then passing to the nitrogen of 150 kPa, the completeest to esterification
Full dioctyl phthalate monomer blocks, and fully opens vacuum pumping valve after the most slowly pressure in still being drawn to-100 kPa
Door, fine vacuum carries out polycondensation reaction, and period temperature in the kettle maintains between 270-275 DEG C；
(3) polycondensation adds ethylene glycol amine latter stage after motor power of agitator reaches certain value again in loading hopper, will charging
Bucket evacuation leads to nitrogen three times, opens hopper valve second time addition ethylene glycol amine and blocks, go out after stirring 2 min after normal pressure
Material, cooling, pelletizing obtain low terminal carboxy content polyester；
(4) gained polyester is obtained low terminal carboxy content polyester after biaxial tension.
Embodiment 4
The low terminal carboxy content polyester of a kind of organic amine end-blocking, the raw material including following quality proportioning synthesizes: terephthaldehyde
Acid 2000 g, ethylene glycol 900 g, antimony glycol 1.2 g, trimethyl phosphate 1.5 g, particle diameter is the silicon dioxide opening agent of 5 μm
3.5 g, add diethanolamine 0.2 g for the first time, and second time adds diethanolamine 1.2 g.
The production method of this ageing-resistant polyester of low terminal carboxy content biaxial tension, comprises the following steps:
(1) p-phthalic acid, ethylene glycol, glycol antimony catalyst, silicon dioxide opening agent and stabilizer are weighed in proportion
Mix homogeneously, joins in 5 L reactors, stirs half an hour, is then shut off stirring, opens vacuum system and slowly extracts oxygen in still out
Gas, is then passed through nitrogen and leads to nitrogen 3 times to normal pressure, repetition evacuation, and then pressurization intensification carries out esterification, and reaction temperature is tieed up
Holding at 230-260 DEG C, in still, pressure maintains about 400kPa, judges esterification degree by process tower top water yield,
After esterification reaches more than 95%, esterification terminates, now in still pressure at 20 below kPa, tower top temperature 100 DEG C with
Under；
(2) after esterification terminates, close process tower valve, in loading hopper, add ethylene glycol amine, loading hopper evacuation is led to
Nitrogen three times, opens hopper valve and adds ethylene glycol amine for the first time after then passing to the nitrogen of 150 kPa, the completeest to esterification
Full dioctyl phthalate monomer blocks, and fully opens vacuum pumping valve after the most slowly pressure in still being drawn to-100 kPa
Door, fine vacuum carries out polycondensation reaction, and period temperature in the kettle maintains between 270-275 DEG C；
(3) polycondensation adds ethylene glycol amine latter stage after motor power of agitator reaches certain value again in loading hopper, will charging
Bucket evacuation leads to nitrogen three times, opens hopper valve second time addition ethylene glycol amine and blocks, go out after stirring 2 min after normal pressure
Material, cooling, pelletizing obtain low terminal carboxy content polyester；
(4) gained polyester is obtained low terminal carboxy content polyester after biaxial tension.
Embodiment 5
The low terminal carboxy content polyester of a kind of organic amine end-blocking, the raw material including following quality proportioning synthesizes: terephthaldehyde
Acid 2000 g, ethylene glycol 900 g, antimony glycol 0.8 g, trimethyl phosphate 1.7 g, particle diameter is the silicon dioxide opening agent 4 of 5 μm
G, adds diethanolamine 0.1 g for the first time, and second time adds diethanolamine 1.5 g.
The production method of this ageing-resistant polyester of low terminal carboxy content biaxial tension, comprises the following steps:
(1) p-phthalic acid, ethylene glycol, glycol antimony catalyst, silicon dioxide opening agent and stabilizer are weighed in proportion
Mix homogeneously, joins in 5 L reactors, stirs half an hour, is then shut off stirring, opens vacuum system and slowly extracts oxygen in still out
Gas, is then passed through nitrogen and leads to nitrogen 3 times to normal pressure, repetition evacuation, and then pressurization intensification carries out esterification, and reaction temperature is tieed up
Holding at 230-260 DEG C, in still, pressure maintains about 400kPa, judges esterification degree by process tower top water yield,
After esterification reaches more than 95%, esterification terminates, now in still pressure at 20 below kPa, tower top temperature 100 DEG C with
Under；
(2) after esterification terminates, close process tower valve, in loading hopper, add ethylene glycol amine, loading hopper evacuation is led to
Nitrogen three times, opens hopper valve and adds ethylene glycol amine for the first time after then passing to the nitrogen of 150 kPa, the completeest to esterification
Full dioctyl phthalate monomer blocks, and fully opens vacuum pumping valve after the most slowly pressure in still being drawn to-100 kPa
Door, fine vacuum carries out polycondensation reaction, and period temperature in the kettle maintains between 265-270 DEG C；
(3) polycondensation adds ethylene glycol amine latter stage after motor power of agitator reaches certain value again in loading hopper, will charging
Bucket evacuation leads to nitrogen three times, opens hopper valve second time addition ethylene glycol amine and blocks, go out after stirring 2 min after normal pressure
Material, cooling, pelletizing obtain low terminal carboxy content polyester；
(4) gained polyester is obtained low terminal carboxy content polyester after biaxial tension.
Embodiment 6
The low terminal carboxy content polyester of a kind of organic amine end-blocking, the raw material including following quality proportioning synthesizes: terephthaldehyde
Acid 2000 g, ethylene glycol 900 g, antimony glycol 1.3 g, trimethyl phosphate 1.7 g, particle diameter is the silicon dioxide opening agent 6 of 5 μm
G, adds diethanolamine 0.3 g for the first time, and second time adds diethanolamine 0.8 g.
The production method of this ageing-resistant polyester of low terminal carboxy content biaxial tension, comprises the following steps:
(1) p-phthalic acid, ethylene glycol, glycol antimony catalyst, silicon dioxide opening agent and stabilizer are weighed in proportion
Mix homogeneously, joins in 5 L reactors, stirs half an hour, is then shut off stirring, opens vacuum system and slowly extracts oxygen in still out
Gas, is then passed through nitrogen and leads to nitrogen 3 times to normal pressure, repetition evacuation, and then pressurization intensification carries out esterification, and reaction temperature is tieed up
Holding at 230-260 DEG C, in still, pressure maintains about 400kPa, judges esterification degree by process tower top water yield,
After esterification reaches more than 95%, esterification terminates, now in still pressure at 20 below kPa, tower top temperature 100 DEG C with
Under；
(2) after esterification terminates, close process tower valve, in loading hopper, add ethylene glycol amine, loading hopper evacuation is led to
Nitrogen three times, opens hopper valve and adds ethylene glycol amine for the first time after then passing to the nitrogen of 150 kPa, the completeest to esterification
Full dioctyl phthalate monomer blocks, and fully opens vacuum pumping valve after the most slowly pressure in still being drawn to-100 kPa
Door, fine vacuum carries out polycondensation reaction, and period temperature in the kettle maintains between 270-278 DEG C；
(3) polycondensation adds ethylene glycol amine latter stage after motor power of agitator reaches certain value again in loading hopper, will charging
Bucket evacuation leads to nitrogen three times, opens hopper valve second time addition ethylene glycol amine and blocks, go out after stirring 2 min after normal pressure
Material, cooling, pelletizing obtain low terminal carboxy content polyester；
(4) gained polyester is obtained low terminal carboxy content polyester after biaxial tension.
The performance test of embodiment 1-embodiment 6 gained low terminal carboxy content polyester is as shown in table 1.
Table 1
The present invention, compared with conventional polyester thin film, drastically increases thermostability, ageing-resistant performance, can increase the service life, with
Time there is higher hot strength, excellent size stability, be used in the field such as construction substrate, solar cell backboard completely.
Simultaneously because rate of ageing delay the prolongation with service life, be also one of approach solving white pollution.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. the low terminal carboxy content polyester of an organic amine end-blocking, it is characterised in that: by the raw material preparation of following quality proportioning
Become: dicarboxylic acid monomer 10000-18000, ethylene glycol 1800-6500, catalyst 1-10, stabilizer 2-10, opening agent 2-50, have
Machine amine 1.3-7.5.
2. the low terminal carboxy content polyester that organic amine blocks as claimed in claim 1, it is characterised in that: dicarboxylic acid monomer is to benzene
Dioctyl phthalate.
3. the low terminal carboxy content polyester that organic amine blocks as claimed in claim 1, it is characterised in that: catalyst is antimony system, titanium
One or more in system or germanium series catalysts.
4. the low terminal carboxy content polyester that organic amine blocks as claimed in claim 1, it is characterised in that: stabilizer is phosphoric acid lipid
Or the combination of the one or both of phosphite apoplexy due to endogenous wind.
5. the low terminal carboxy content polyester of as claimed in claim 1 organic amine end-blocking, it is characterised in that: opening agent be barium sulfate,
One or more in calcium carbonate or silicon dioxide.
6. the low terminal carboxy content polyester that organic amine blocks as claimed in claim 1, it is characterised in that: organic amine is three ethanol
One or more in amine, diethanolamine or ethylenediamine.
7. the preparation method of the low terminal carboxy content polyester of an organic amine as claimed in claim 1 end-blocking, it is characterised in that: bag
Include following steps:
(1), dioctyl phthalate monomer, ethylene glycol, catalyst, opening agent and stabilizer being mixed in proportion, it is anti-that heating carries out esterification
Should, judge esterification degree by water yield, after esterification reaches more than 95%, terminate esterification；
(2), in step (1) esterification reaction product, add part organic amine, carry out polycondensation reaction under a high vacuum；
, step (2) polycondensation reaction latter stage, add remaining organic amine and block, obtain low terminal carboxy content polyester.
8. preparation method as claimed in claim 7, it is characterised in that: the low terminal carboxy content polyester prepared is at biaxial tension
Reason.
9. as claimed in claim 7 preparation method, it is characterised in that: step (2) in, the quality proportioning of organic amine is 0.3-
0.5。
10. as claimed in claim 7 preparation method, it is characterised in that: step (3) in, the quality proportioning of organic amine is 1-7.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108676152A (en) * | 2018-04-02 | 2018-10-19 | 哈尔滨工业大学无锡新材料研究院 | A kind of the wet and heat ageing resistant polyester film and its synthetic method of multi-group epoxy compound's sealing end |
| CN110041515A (en) * | 2019-05-22 | 2019-07-23 | 无锡风鹏新材料科技有限公司 | A kind of polyester film and preparation method thereof for medical package of uncoated processing |
| CN114621420A (en) * | 2020-12-14 | 2022-06-14 | 彤程化学（中国）有限公司 | Biodegradable aliphatic-aromatic copolyester and synthesis method thereof |
| WO2023221932A1 (en) * | 2022-05-17 | 2023-11-23 | 扬州纳力新材料科技有限公司 | Polyester base film, preparation method therefor and application thereof, pole piece, and lithium battery cell |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108676152A (en) * | 2018-04-02 | 2018-10-19 | 哈尔滨工业大学无锡新材料研究院 | A kind of the wet and heat ageing resistant polyester film and its synthetic method of multi-group epoxy compound's sealing end |
| CN108676152B (en) * | 2018-04-02 | 2020-07-07 | 哈尔滨工业大学无锡新材料研究院 | Polyfunctional epoxy compound-terminated polyester film resistant to heat and humidity aging and synthesis method thereof |
| CN110041515A (en) * | 2019-05-22 | 2019-07-23 | 无锡风鹏新材料科技有限公司 | A kind of polyester film and preparation method thereof for medical package of uncoated processing |
| CN114621420A (en) * | 2020-12-14 | 2022-06-14 | 彤程化学（中国）有限公司 | Biodegradable aliphatic-aromatic copolyester and synthesis method thereof |
| WO2022126812A1 (en) * | 2020-12-14 | 2022-06-23 | 彤程化学（中国）有限公司 | Biodegradable aliphatic-aromatic copolyester and synthesis method therefor |
| WO2023221932A1 (en) * | 2022-05-17 | 2023-11-23 | 扬州纳力新材料科技有限公司 | Polyester base film, preparation method therefor and application thereof, pole piece, and lithium battery cell |
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| CN106220835B (en) | 2018-05-15 |
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